CN104177523A - Polypropylene catalyst spherical carrier and solid catalyst and preparation method thereof - Google Patents
Polypropylene catalyst spherical carrier and solid catalyst and preparation method thereof Download PDFInfo
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- CN104177523A CN104177523A CN201410442508.7A CN201410442508A CN104177523A CN 104177523 A CN104177523 A CN 104177523A CN 201410442508 A CN201410442508 A CN 201410442508A CN 104177523 A CN104177523 A CN 104177523A
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- magnesium chloride
- ball type
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- type carrier
- silica gel
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a polypropylene catalyst spherical carrier and a solid catalyst and a preparation method thereof. The preparation method comprises the following steps: carrying out a heating reaction between a magnesium chloride alcohol compound formed by complexing magnesium chloride and alcohol and fumed silica in a dispersing medium, and forming uniform slurry containing the magnesium chloride alcohol compound; dispersing the slurry in an inert dispersing medium under the high shearing action, introducing the slurry into a low-temperature inert dispersing medium, and carrying out freeze curing to form the spherical particle carrier containing the magnesium chloride alcohol compound. A solid catalyst prepared by adopting the carrier is used for olefin polymerization, namely propylene polymerization, and has relatively high polymerization activity, relatively low fine powder content and good polymer particle form.
Description
Technical field
The present invention relates to a kind of ball type carrier and solid polypropylene catalyzer prepared therefrom, be specifically related to a kind of ball type carrier and solid polypropylene catalyzer prepared therefrom that comprises that magnesium chloride, alcohol and smoke-like silica gel form.
Background technology
In prior art, the preparation method of disclosed spherical magnesium chloride support has a variety of, as high-speed mixing method, tubule extrusion molding, gravity Method, spray cooling and spray-drying process etc., while adopting catalyzer prepared by these methods for olefinic polymerization, easily there is Fragmentation Phenomena and cause fine polymer powder on the high side, its reason may have multiple: the one, and the physical strength of support/catalyst is on the low side, Er Shi catalyst active center skewness, in polymerization process, the polymerization rate at each position of catalyzer seriously differs and causes polymer beads internal stress uneven.
The magnesium chloride support of being prepared by spray-drying process in prior art, due to organic solvent in drying process (as alcohol) Quick-gasifying, granule interior primary particle is in conjunction with undertighten, and the physical strength of carrier is lower, and mean pore size is larger, porosity is higher, and easily form more hollow-particle, catalyzer prepared therefrom has copied such grain pattern, therefore the polymer beads fine powder content being obtained by this class polymerization catalyst is higher, tap density is on the low side, is generally less than 0.40g/cm
3.When the catalyzer that adopts existing spherical magnesium chloride support to prepare is during for olefinic polymerization, will have a strong impact on polymerization activity and taxis, and directly affect the quality of resulting polymers.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of polypropylene catalyst ball type carrier, its solid catalyst and preparation method thereof, comprise magnesium chloride alcohol adduct and smoke-like silica gel that magnesium chloride and alcohol complexing form, that the liquid form mixt that contains magnesium chloride alcohol adduct and smoke-like silica gel is dispersed in the dispersion medium forming with the inconsistent mineral oil of this alcohol adduct and silicone oil through high shear forces, then be incorporated in low temperature inert media, the freezing spheroidal particle that solidify to form magnesium chloride containing alcohol adduct, the solid catalyst that adopts this carrier to prepare, for olefinic polymerization particularly during propylene polymerization, shown higher polymerization activity, lower fine powder content and good morphology.
Concrete technical scheme of the present invention is:
A kind of polypropylene catalyst ball type carrier, comprise magnesium chloride alcohol adduct and smoke-like silica gel that magnesium chloride and alcohol complexing form, that the liquid form mixt that contains magnesium chloride alcohol adduct and smoke-like silica gel is dispersed in the dispersion medium forming with the inconsistent mineral oil of this alcohol adduct and silicone oil through high shear forces, then be incorporated in low temperature inert media the freezing spheroidal particle that solidify to form magnesium chloride containing alcohol adduct.
Described magnesium chloride alcohol adduct is as formula M gCl
2shown in-mROH (I);
In formula I, R is C
1-C
10alkyl or C
3-C
10cycloalkyl or C
6-C
10aryl; In formula I, m is 1-5; Preferred 2.0-3.0;
Described alcohol is a kind of in methyl alcohol or ethanol or n-propyl alcohol or Virahol or propyl carbinol or isopropylcarbinol, is preferably ethanol.
Described smoke-like silica gel is the silica gel that the median size of being produced by vapor phase process is less than 1 μ m, is preferably the nano level silica gel that median size is less than 100nm, is commercially available prod, as the TS-610 of Cabot company, TS-530D, TS-720D.Described smoke-like silica gel is surface treated hydrophobic silicone, after hydrophobic treatment, both has good consistency with magnesium chloride alcohol adduct molten mass, has avoided again the existence of great amount of hydroxy group to cause negative impact to performances such as polymerization catalyst activity.
The preparation method of described polypropylene catalyst ball type carrier, concrete steps comprise:
(a) first by magnesium chloride, alcohol and smoke-like silica gel contact reacts under the condition of heating and the existence of mineral oil dispersion medium, form the slurries of the magnesium chloride containing alcohol adduct of homogeneous;
(b) slurries of magnesium chloride containing alcohol adduct step (a) being obtained contact with the silicone oil dispersion medium that is preheated to 100-140 ℃, then to have the mode of high shear forces, said mixture are fully disperseed, and are dispersed into two phase emulsion.
Further, in order to reduce operation steps, described step (a) and step (b) can union operation be step (1), that is:
(1) contact reacts under the condition first magnesium chloride, alcohol and smoke-like silica gel being existed at the dispersion medium that heats and be comprised of mineral oil and silicone oil, then fully disperses said mixture to have the mode of high shear forces, is dispersed into two phase emulsion;
(2) by step (1) in the two phase emulsion of the good magnesium chloride containing alcohol adduct of dispersion treatment sprays into rapidly cooling good low temperature inert media, the freezing spheroidal particle that solidify to form magnesium chloride containing alcohol adduct.
In described polypropylene catalyst ball type carrier, the mol ratio of magnesium chloride and alcohol is 2.0-3.0.
In described spheric polypropylene catalyst carrier, the mass ratio of magnesium chloride and fumed silica is 6-1.
Reacting by heating described in step (1) is temperature required is 100 ℃-140 ℃.
Mineral oil described in step (1) is the mineral oil through hydrofining processing and dehydration refinement treatment, and described mineral oil is selected from one or more of white oil or vaseline oil or whiteruss or kerosene.
Silicone oil described in step (1) is methyl-silicone oil, and being preferably viscosity is the methyl-silicone oil of 200-500 centipoise (20 ℃).
Described in step (1), the volume ratio of silicone oil and mineral oil is 1-10:1.
High shear forces mode described in step (1) is selected from a kind of of high-speed mixing method or mulser emulsion process or gravity Method or spray cooling, be preferably a kind of of high-speed mixing method or mulser emulsion process or gravity Method, further, be preferably high-speed mixing method.
Described in step (1), the add-on of dispersion medium is 1-100mL/g magnesium chloride.
The described low temperature inert media of step (2) is C
5-C
10inertia alkane or C
6-C
10inertia naphthenic hydrocarbon or C
6-C
10inertia aromatic hydrocarbons in one or more, be preferably one or both of hexane or heptane.
The temperature of the described cooling low temperature inert media of step (2) is-40 ℃-10 ℃.
Further, in order to obtain the better ball type carrier of mobility, concrete steps also comprise with inert media washs this spheroidal particle, that is: adopt inert media at room temperature to wash the spheroidal particle of the magnesium chloride containing alcohol adduct of step (2) gained, vacuum-drying at 30-50 ℃, obtains ball type carrier.Wherein, described inert media can be identical with the described low temperature inert media of step (2), also can be different, from effect and price factor, consider, and be preferably hexane, its consumption is 5-10mL/g particulate matter.
The polypropylene catalyst that adopts described ball type carrier to prepare, be by by least one halogenated titanium, at least one electron donor is compound loaded on the ball type carrier of described magnesium chloride containing alcohol adduct, obtains.
The polypropylene catalyst that adopts ball type carrier of the present invention to prepare, its particle median size is between 10-100 μ m, and preferably, between 25-80 μ m, specific surface area is greater than 300m
2/ g; In described catalyzer, titanium content is 1-4wt%, preferably at 1.5-3.0wt%; The content of electron donor is 5-16wt%.
Described halogenated titanium is selected from TiCl
4and TiBr
4, preferred TiCl
4.
One or more of the phenylene aromatic diesters class that described electron donor compound is replacement or phthalate or two ethers or succinate compound or diol-lipid compound.
The polypropylene catalyst that adopts described ball type carrier to prepare, its preparation method carries out according to ordinary method of the prior art.As: the ball type carrier of magnesium chloride containing alcohol adduct of the present invention is under agitation contacted with cooling good low temperature titanium tetrachloride (0 ℃ to-30 ℃), contact and after 30 minutes to 48 hours, be warming up to 80-130 ℃ and continue reaction.During contact, can, with inert solvent as reaction medium, also can use titanium tetrachloride itself as reaction medium.Then add electron donor compound and titanium tetrachloride to be further processed the solid of gained, also can be after titanium tetrachloride be processed, use again electron donor compound individual curing, finally by filtering, wash, be dried the spherical catalyst that obtains solid powdery.
Polypropylene catalyst ball type carrier of the present invention, is that the magnesium chloride alcohol adduct and the smoke-like silica gel that comprise magnesium chloride and alcohol complexing formation are carried out to reacting by heating in inert dispersion medium, forms the slurries of the magnesium chloride containing alcohol adduct of homogeneous; Through high shear forces, be dispersed in dispersion medium again, then be incorporated in low temperature inert media, the freezing spheroidal particle carrier that solidify to form magnesium chloride containing alcohol adduct, the solid catalyst that adopts this carrier to prepare, for olefinic polymerization particularly during propylene polymerization, shown higher polymerization activity, lower fine powder content and good morphology.
Embodiment
Embodiment 1
(1) carrier preparation
Take white oil as medium, add 47.6g magnesium chloride and 59.8g ethanol (mol ratio of ethanol and magnesium chloride is 2.6/1), (Cabot company's T S-610, through hot N for 15g smoke-like silica gel
2blow and get rid of except free-water), white oil consumption is 286mL, white oil viscosity is 30 centipoises (20 ℃), reacts 2.5 hours at 125 ℃.
The slurries containing what thing of molten polyol and smoke-like silica gel that above-mentioned reaction is obtained are transferred in the preheated methyl-silicone oil medium of 125 ℃; The viscosity of methyl-silicone oil is 300 centipoises (20 ℃), and the consumption of methyl-silicone oil is 572mL; With the rotating speeds of 2500 revs/min, stir 15 minutes.
The tubule that is 45 by length-to-diameter ratio is with the flow of 300mL/min, and the slurries that above-mentioned height stirred to dispersion are transferred in advance in the hexane medium that is cooled to-30 ℃, with the rotating speeds of 300 revs/min, stirs 15 minutes, and the volume ratio of hexane and slurries is 4:1.
From chilling, in the suspension of gained, filter out solid particulate matter; With hexane, at room temperature wash this particulate matter, hexane consumption is 5-10mL/g particulate matter, washs altogether 6 times; At 30-50 ℃, vacuumize dryly, obtain spheroidal particle thing.In the ball type carrier that the thermogravimetry analysis of take prepares, the mol ratio of ethanol and magnesium chloride is 2.6.
(2) spherical solid catalyst component preparation
In reaction flask, add 100mLTiCl
4, be cooled to-20 ℃, at-20 ℃, add the ball type carrier of the magnesium chloride containing alcohol adduct of the above-mentioned preparation of 7g; Slowly be warming up to afterwards 100 ℃, and add 1.4mLDIBP in the time of 40 ℃, at 100 ℃, maintain reaction 2 hours, rear filtered while hot, then add 100mLTiCl
4, be warming up to 125 ℃, at 125 ℃, maintain reaction 2 hours, rear filtered while hot; With hexane, wash 4 times at 50-60 ℃, at room temperature wash 2 times, each hexane consumption is 60mL.Then be dried and obtain spherical solid catalyst component.
(3) propylene polymerization
At 70 ℃, by propylene gas, 2L stainless steel high pressure polymerisation reactor is purged to 1 hour, at room temperature, to add 1mL concentration in nitrogen atmosphere be the triethyl aluminium solution of 1mol/L, hexane solution and the above-mentioned ingredient of solid catalyst making of 9mg of Cyclohexyl Methyl Dimethoxysilane that 0.5mL concentration is 0.1mol/L.The hydrogen and the 1L liquid propene that add 4NL (standard liter).Under agitation condition, be warming up to 70 ℃ in 5 minutes. at this temperature, reacted 1 as a child, stopped stirring emptying discharging.Catalyst performance and polymer powders the performance test results are in Table 1 and table 2.
Embodiment 2
(1) carrier preparation
Except smoke-like silica gel add-on is 5g, the other the same as in Example 1.In the ball type carrier that the thermogravimetry analysis of take prepares, the mol ratio of ethanol and magnesium chloride is 2.6.
(2) spherical solid catalyst component preparation
With embodiment 1.
(3) propylene polymerization
With embodiment 1.Catalyst performance and polymer powders the performance test results are in Table 1 and table 2.
Embodiment 3
(1) carrier preparation
Except adding 47.6g magnesium chloride and 69g ethanol (mol ratio of ethanol and magnesium chloride is 3.0/1.0), the other the same as in Example 1.In the ball type carrier that the thermogravimetry analysis of take prepares, the mol ratio of ethanol and magnesium chloride is 3.0.
(2) spherical solid catalyst component preparation
With embodiment 1.
(3) propylene polymerization
With embodiment 1.Catalyst performance and polymer powders the performance test results are in Table 1 and table 2.
Embodiment 4
(1) carrier preparation
Except adding 47.6g magnesium chloride and 69g ethanol (mol ratio of ethanol and magnesium chloride is 3/1), the other the same as in Example 1.In the ball type carrier that the thermogravimetry analysis of take prepares, the mol ratio of ethanol and magnesium chloride is 3.
(2) spherical solid catalyst component preparation
With embodiment 1.
(3) propylene polymerization
With embodiment 1.Catalyst performance and polymer powders the performance test results are in Table 1 and table 2.
Comparative example 1
(1) carrier preparation
Except not adding smoke-like silica gel, the other the same as in Example 1.In the ball type carrier that the thermogravimetry analysis of take prepares, the mol ratio of ethanol and magnesium chloride is 2.6.
(2) spherical solid catalyst component preparation
With embodiment 1.
(3) propylene polymerization
With embodiment 1.Catalyst performance and polymer powders the performance test results are in Table 1 and table 2.
Comparative example 2
(1) carrier preparation
The preparation of mother liquor for magnesium chloride spraying: at process N
2in the 350mL reactor that fully band of displacement stirs, add 200mL through the ethanol of processed, under room temperature, add while stirring 17g Magnesium Chloride Anhydrous, control the speed that adds of magnesium chloride, system temperature is remained on below 40 ℃, after magnesium chloride adds, mixed system temperature is risen to 70 ℃, and this temperature constant temperature 4 hours, obtain even MgCl
2ethanolic soln.17g smoke-like silica gel is joined in above-mentioned solution under the condition of rapid stirring, continue to maintain original temperature rapid stirring more than 1.5 hours, obtain spraying standby with mother liquor.
The dry preparation of spraying MgCl
2/ SiO
2complex carrier: use peristaltic pump that the mother liquor obtaining in a) step is incorporated into two-fluid spray nozzle by pipeline, atomization enters kiln.Control feed liquid and spray gas N
2flow is respectively 18mL/min and 350L/h, and spraying temperature degree is room temperature.Carrier gas N
2flow control is at 7200L/min place, and instrument inlet port temperature is 190 ℃, and correspondingly instrument temperature out is stabilized near 97 ℃.In the exit, below of cyclonic separator, collect and obtain spherical MgCl
2/ SiO
2complex carrier particle.In the ball type carrier that the thermogravimetry analysis of take prepares, the mol ratio of ethanol and magnesium chloride is 0.69.
(2) spherical solid catalyst component preparation
With embodiment 1.
(3) propylene polymerization
With embodiment 1.Catalyst performance and polymer powders the performance test results are in Table 1 and table 2.
Table 1 catalyst performance
The size distribution of table 2 polymkeric substance
As shown in Table 1, shown higher polymerization activity, and the polymer bulk density obtaining is higher while having catalyzer prepared by ball type carrier of the present invention for propylene polymerization, taxis also satisfies the demands.
As shown in Table 2, while having catalyzer prepared by ball type carrier of the present invention for propylene polymerization, resulting polymers powder fine powder is less, shows that polymer particle broken in polymerization process obviously reduces.
Claims (16)
1. a polypropylene catalyst ball type carrier, comprise magnesium chloride alcohol adduct and smoke-like silica gel that magnesium chloride and alcohol complexing form, that the liquid form mixt that contains magnesium chloride alcohol adduct and smoke-like silica gel is dispersed in the dispersion medium forming with the inconsistent mineral oil of this alcohol adduct and silicone oil through high shear forces, then be incorporated in low temperature inert media the freezing spheroidal particle that solidify to form magnesium chloride containing alcohol adduct;
Described magnesium chloride alcohol adduct is as formula M gCl
2shown in-mROH (I);
In formula I, R is C
1-C
10alkyl or C
3-C
10cycloalkyl or C
6-C
10aryl; In formula I, m is 1-5;
Described smoke-like silica gel, the median size of being produced by vapor phase process is less than the silica gel of 1 μ m.
2. ball type carrier according to claim 1, is characterized in that: described alcohol is ethanol, and in the logical formula I of described magnesium chloride alcohol adduct, m is 2.0-3.0.
3. ball type carrier according to claim 1, is characterized in that: described smoke-like silica gel is surface treated hydrophobic silicone.
4. ball type carrier according to claim 1, is characterized in that: described mineral oil is selected from one or more of white oil or vaseline oil or whiteruss or kerosene.
5. ball type carrier according to claim 1, is characterized in that: described silicone oil is methyl-silicone oil.
6. ball type carrier according to claim 1, is characterized in that: described high shear forces mode is selected from a kind of of high-speed mixing method or mulser emulsion process or gravity Method or spray cooling.
7. according to the ball type carrier described in claim 1 or 6, it is characterized in that: described high shear forces mode is selected from a kind of of high-speed mixing method or mulser emulsion process or gravity Method.
8. according to the ball type carrier described in claim 1 or 7, it is characterized in that, described high shear forces mode is high-speed mixing method.
9. the preparation method of ball type carrier as claimed in claim 1, is characterized in that: concrete steps comprise:
(1) contact reacts under the condition first magnesium chloride, alcohol and smoke-like silica gel being existed at the dispersion medium that heats and be comprised of mineral oil and silicone oil, then fully disperses said mixture to have the mode of high shear forces, is dispersed into two phase emulsion;
(2) by step (1) in the two phase emulsion of the good magnesium chloride containing alcohol adduct of dispersion treatment sprays into rapidly cooling good low temperature inert media, the freezing spheroidal particle that solidify to form magnesium chloride containing alcohol adduct;
Described magnesium chloride alcohol adduct is as formula M gCl
2shown in-mROH (I);
In formula I, R is C
1-C
10alkyl or C
3-C
10cycloalkyl or C
6-C
10aryl; In formula I, m is 1-5;
Described smoke-like silica gel, the median size of being produced by vapor phase process is less than the silica gel of 1 μ m.
10. the preparation method of ball type carrier according to claim 9, is characterized in that: also comprise with inert media and wash this spheroidal particle.
The preparation method of 11. ball type carriers according to claim 9, is characterized in that: in the logical formula I of described magnesium chloride alcohol adduct, m is 2.0-3.0.
The preparation method of 12. ball type carriers according to claim 9, is characterized in that: described mineral oil is selected from one or more of white oil or vaseline oil or whiteruss or kerosene.
The preparation method of 13. ball type carriers according to claim 9, is characterized in that: the contact reacts temperature described in step (1) is 100-140 ℃.
The preparation method of 14. ball type carriers according to claim 9, is characterized in that: the mode of the high shear forces described in step (1) is selected from a kind of of high-speed mixing method or mulser emulsion process or gravity Method or spray cooling.
The preparation method of 15. ball type carriers according to claim 9, is characterized in that: the mode of the high shear forces described in step (1) is selected from a kind of of high-speed mixing method or mulser emulsion process or gravity Method.
16. 1 kinds of spherical solid catalyst components for propylene polymerization are to obtain by least one halogenated titanium of load on ball type carrier claimed in claim 1 and at least one electron donor compound.
Priority Applications (1)
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|---|---|---|---|
| CN201410442508.7A CN104177523A (en) | 2014-09-02 | 2014-09-02 | Polypropylene catalyst spherical carrier and solid catalyst and preparation method thereof |
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|---|---|---|---|
| CN201410442508.7A CN104177523A (en) | 2014-09-02 | 2014-09-02 | Polypropylene catalyst spherical carrier and solid catalyst and preparation method thereof |
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ID=51958888
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107722151A (en) * | 2017-10-18 | 2018-02-23 | 兰州石化职业技术学院 | A kind of preparation method of high modulus polypropylene |
| CN107814858A (en) * | 2017-10-18 | 2018-03-20 | 兰州石化职业技术学院 | A kind of preparation method of complex carrier polypropylene catalyst |
| CN109694425A (en) * | 2017-10-24 | 2019-04-30 | 中国石油化工股份有限公司 | Catalytic component for olefinic polymerization and preparation method thereof and catalyst and its application |
| CN110467694A (en) * | 2018-05-09 | 2019-11-19 | 中国石油天然气股份有限公司 | Preparation method, propylene high-temperature polymerization catalyst component and the propylene high-temperature polymerization catalyst of propylene high-temperature polymerization catalyst complex carrier |
| CN113004445A (en) * | 2021-03-29 | 2021-06-22 | 淄博新塑化工有限公司 | Regular carrier of polypropylene catalyst, preparation method thereof and polypropylene catalyst prepared by regular carrier |
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| CN1524886A (en) * | 2003-02-24 | 2004-09-01 | 中国石油化工股份有限公司 | Compound carrier for olefin polymerization catalyst, catalyst components and the catalyst |
| CN102432706A (en) * | 2011-09-15 | 2012-05-02 | 中国石油天然气股份有限公司 | Composite magnesium chloride spherical carrier, preparation and application |
| CN102558398A (en) * | 2010-12-30 | 2012-07-11 | 中国石油化工股份有限公司 | Method for preparing spherical magnesium chloride carrier |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1524886A (en) * | 2003-02-24 | 2004-09-01 | 中国石油化工股份有限公司 | Compound carrier for olefin polymerization catalyst, catalyst components and the catalyst |
| CN102558398A (en) * | 2010-12-30 | 2012-07-11 | 中国石油化工股份有限公司 | Method for preparing spherical magnesium chloride carrier |
| CN102432706A (en) * | 2011-09-15 | 2012-05-02 | 中国石油天然气股份有限公司 | Composite magnesium chloride spherical carrier, preparation and application |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107722151A (en) * | 2017-10-18 | 2018-02-23 | 兰州石化职业技术学院 | A kind of preparation method of high modulus polypropylene |
| CN107814858A (en) * | 2017-10-18 | 2018-03-20 | 兰州石化职业技术学院 | A kind of preparation method of complex carrier polypropylene catalyst |
| CN109694425A (en) * | 2017-10-24 | 2019-04-30 | 中国石油化工股份有限公司 | Catalytic component for olefinic polymerization and preparation method thereof and catalyst and its application |
| CN109694425B (en) * | 2017-10-24 | 2021-10-19 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, preparation method thereof, catalyst and application thereof |
| CN110467694A (en) * | 2018-05-09 | 2019-11-19 | 中国石油天然气股份有限公司 | Preparation method, propylene high-temperature polymerization catalyst component and the propylene high-temperature polymerization catalyst of propylene high-temperature polymerization catalyst complex carrier |
| CN110467694B (en) * | 2018-05-09 | 2022-01-04 | 中国石油天然气股份有限公司 | Preparation method of composite carrier of propylene high-temperature polymerization catalyst, propylene high-temperature polymerization catalyst component and propylene high-temperature polymerization catalyst |
| CN113004445A (en) * | 2021-03-29 | 2021-06-22 | 淄博新塑化工有限公司 | Regular carrier of polypropylene catalyst, preparation method thereof and polypropylene catalyst prepared by regular carrier |
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Application publication date: 20141203 |